Synthesis and Photophysical Properties of 3-Substituted-1H-Indazoles: A Pd-Catalyzed Double C-N Bond Formation Strategy via 1,6-Conjugate Addition.

A Pd-catalyzed cascade process for the direct synthesis of 3-substituted-1H-indazole employing p-quinone methide (p-QM) and arylhydrazine through Pd-catalyzed double C-N bond formation via 1,6-conjugate addition is reported. This reaction strategy affords efficient and practical access to synthetically important diverse 3-substituted-1H-indazoles in good yields. The photophysical properties of the synthesized 3-substituted-1H-indazoles are investigated, and some of them showed very good fluorescence properties with quantum yields up to 85%. Also, the synthesized 3-substituted-1H-indazole exhibits an acid-sensitive fluorescence turn-off activity.

Novel fibrous Ag(NP) decorated clay-polymer composite: Implications in water purification contaminated with predominant micro-pollutants and bacteria.

Due to the potential harm caused by emerging micro-pollutants to living organisms, contaminating water supplies by micro-pollutants like EDCs, pharmaceuticals, and microorganisms has become a concern in many countries. Considering both microbiological and micro-pollutant exposure risks associated with water use for agricultural/or household purposes, it is imperative to create a strategy for improving pollutant removal from treated wastewater that is both effective and affordable. Natural clay minerals efficiently remove contaminants from wastewater, though the pristine clay has less affinity to several organic pollutants. Hydrophilic polymers, viz., poly(ethylene glycol) (PEG), improve the dispersion of particles, flocculation processes, and surface properties. In this study, PEG grafted with attapulgite, thereby providing a high-specific surface-area, mesoporous materials for the adsorption of micro-pollutants like ciprofloxacin (CIP) and 17α-ethinylestradiol (EE2) at high rates. A gentle washing process regenerates the clay-polymer material several times with no performance loss, and the natural water implications show fair applicability of solid in decontaminating the CIP and EE2 in an aqueous medium. Further, greenly synthesized silver nanoparticles in situ disperse with the clay polymer efficiently remove the gram-positive and gram-negative bacterium viz., Bacillus subtilis, and Pseudomonas aeruginosa, which are commonly persistent in aquatic environments. The clay polymer outperformed a modified clay composite to eliminate microorganisms and organic micro-pollutants in significant quantities quickly. These results clearly show the importance of fibrous clay-polymer composite for water purification technologies.

Synthesis of π-Extended Benzofulvenes: A Pd-Catalyzed Cascade Annulation Process Comprising C-C Bond Formation Followed by 1,6-Conjugate Addition.

A Pd-catalyzed cascade annulation process comprising C-C bond formation followed by 1,6-conjugate addition for π-extended benzofulvenes is reported. This process is compatible with a wide range of functionalities for both the p-quinone methides and internal alkynes, leading to diverse π-extended benzofulvenes. Additionally, this strategy is also applicable for aryne annulation with p-quinone methides.

Pd-Catalyzed Alkyne and Aryne Annulations: Synthesis and Photophysical Properties of π-Extended Coumarins.

A Pd-catalyzed alkyne and aryne annulation strategy via C-H activation has been implemented for the synthesis of π-extended coumarins. This synthetic strategy provides a wide range of π-extended coumarins in moderate to good yields with good functional group compatibility. Photophysical properties of the synthesized π-extended coumarins have been evaluated, and some of them show interesting fluorescent properties. Three of the synthesized coumarins have been unambiguously established by a single-crystal XRD study.

Copper-Catalyzed Direct Syntheses of Phenoxypyrimidines from Chloropyrimidines and Arylboronic Acids: A Cascade Avenue and Unconventional Substrate Pairs.

This letter describes the first synthetic methodology for phenoxypyrimidines that avoids the direct use of phenols or their salts. In contrast to the general trend of delivering Suzuki-Miyaura cross-coupling products in reactions between aryl or alky halides and arylboronic acids, the substrate pairs used herein (chloropyrimidines and arylboronic acids) led to C-O bond formation under the reaction conditions. In total, 25 phenoxypyrimidines were successfully synthesized using the described protocol, 6 of which had a structural resemblance to etravirine.

Carbon nanotubes ornamented hollow polymethyl methacrylate microspheres for turbidity removal from water.

Novel materials with low density are being synthesized with great interest owing to their effectiveness in water purification systems. Materials of micro/nano-scale provide outstanding results in miniature point-of-use devices because of their high surface-to-volume ratio. In this study, we report the successful synthesis of hollow polymethyl methacrylate microspheres (HPM) coated with functionalized carbon nanotubes (f-CNTs) (CHPM) by employing solvent evaporation and in situ coating techniques. The surface coating of HPM with the f-CNTs was visually confirmed by the surface roughness recorded in scanning electron microscopy. Furthermore, characterization with Fourier transform infrared spectroscopy substantiated the presence of hydroxyl and carboxyl groups of f-CNTs on the CHPM. The efficiency of CHPM to remove the turbidity from surface water was evaluated. The CHPM was effective in bringing down the turbidity of the water from 500 NTU to <1 NTU (>97%) which was within the desirable limit of the Bureau of Indian Standards. The temperature and pH for maximum reduction in turbidity were optimized to 49.5 °C and 4.5, respectively. Moreover, kinetic studies of CHPM indicated that the material followed the Langmuir isotherm model with regeneration efficiency lasting more than 10 cycles. From the results, we propose a simple, facile, and cost-effective synthetic route for the synthesis of CHPM for water purification, especially for turbidity removal. The synthesized CHPM with low density and relatively large surface area offer huge potential in water treatment applications and related fields.

Overview of coumarin-fused-coumarins: synthesis, photophysical properties and their applications.

Coumarin-fused-coumarins have attracted significant attention in the scientific world owing to their boundless applications in interdisciplinary areas. Various synthetic pathways have been developed to construct novel coumarin-fused-coumarin analogues by the fusion of modern methodologies with a classical Pechmann reaction or Knoevenagel condensation. Owing to their extended molecular framework, they possess interesting photophysical properties depending on the fused coumarin ring systems. This review highlights previously published reports on the synthetic strategies for structurally diverse coumarin-fused-coumarins. Furthermore, the scope of the synthesized biscoumarin-fused entities is described by highlighting their photophysical properties and applications.

A palladium-catalyzed cascade process for spirooxindole: an alternative way for the synthesis of spiro(indoline-3,2'-quinazolin)-2-ones.

A palladium-catalyzed cascade strategy has been developed for one-pot synthesis of functionalized spiro(indoline-3,2'-quinazolin)-2-one derivatives from readily available starting materials. The reaction proceeds via C-C and two C-N bond formations in a single reaction operation. This method offers an attractive pathway for the synthesis of a broad range of spiro(indoline-3,2'-quinazolin)-2-ones in good yields.

Aryne insertion into the P[double bond, length as m-dash]O bond: one-pot synthesis of quaternary phosphonium triflates.

A novel transition-metal free synthetic strategy has been developed for the direct synthesis of quaternary phosphonium triflates via insertion of aryne into phosphine oxide. This methodology provides good yields of quaternary phosphonium salts and one of the synthesized phosphonium salts has been unambiguously established by single crystal XRD study. Preliminary mechanistic studies suggest that the reaction proceeds via a sequential [2 + 2] cycloaddition followed by the o-arylation and protonation pathway.

Highly efficient hydrophobic nanocomposite in the decontamination of micropollutants and bacteria from aqueous wastes: A sustainable approach.

Micro-pollutants (specifically antibiotics and personal care products) and potential bacterial contamination pose a severe threat to human health and marine life. The study derives indigenous novel fibrous hydrophobic nanocomposite, efficient in decontaminating the micro-pollutants (tetracycline (TC) and bisphenol A (BPA)) and potential pathogens (S. pyogenes and E. coli) from aqueous wastes. A facile method synthesizes the fibrous attapulgite (ATP)- poly(4-vinylpyridine-co-styrene) (PVP) framework decorated in situ with the Ag0 nanoparticles (ATP@PVP/Ag0). A greener method using the Artocarpus heterophyllus leaf extract derives the Ag0(NPs). Various analytical methods extensively characterize the materials. A comprehensive study that includes pH, concentration, background electrolytes, and ionic strength reveals the sorptive removal insights of TC and BPA utilizing the ATP@PVP solid. The elimination of tetracycline (TC) and bisphenol A (BPA) agrees well with the pseudo-second-order kinetics. The pH 3.07 and 6.06 favor removing TC and BPA with the capacity of 10.86 mg/g and 17.36 mg/g at 25 °C. The hydrogen bonding and hydrophobic interactions predominate the sorption mechanism, and the material shows remarkable stability and reusability in repeated sorption/desorption operations. Similarly, the natural water implications and flow-bed system show fair applicability of solid in decontaminating the TC and BPA in an aqueous medium. Further, the material ATP@PVP/Ag0 exhibits very high inhibition of potential pathogens S. pyogenes and E. coli and optimizes the solid dose and solution pH.

Mitochondria-targeted biotin-conjugated BODIPYs for cancer imaging and therapy.

Two BODIPY-biotin conjugates KDP1 and KDP2 are designed and synthesized for targeted PDT applications. Both have good absorption with a high molar absorption coefficient and decent singlet oxygen generation quantum yields. The photosensitizers KDP1 and KDP2 were found to be localized in the mitochondria with excellent photocytotoxicity of up to 18.7 nM in MDA-MB-231 breast cancer cells. The cell death predominantly proceeded through the apoptosis pathway via ROS production.

Acrylonitrile adducts: design, synthesis and biological evaluation as antimicrobial, haemolytic and thrombolytic agent.

In this work, five acrylonitrile adducts were screened for antibacterial activity against Gram-positive Bacillus subtilis, Microbial Type Culture Collection and Gene Bank (MTCC 1305) and Gram-negative Escherichia coli (MTCC 443). Synthesis was followed by aza-Michael addition reaction, where the acrylonitrile accepts an electron pair from the respective amines and results in the formation of n-alkyliminobis-propionitrile and n-alkyliminopropionitrile under microwave irradiation. Characterization of the compounds were performed using Fourier Transform Infrared (FTIR), Proton Nuclear Magnetic Resonance (1H NMR) and Electrospray Ionisation Mass Spectrometry (ESI-MS). The particle size characterization was done by Dynamic Light Scattering (DLS) technique. The antibacterial study showed higher inhibition rate for both Gram-positive and Gram-negative bacteria. The antibacterial ability was found to be dose dependent. The minimum inhibitory concentration against both bacteria were found to be 1, 3, 0.4, 1, 3 µl/ml for E. coli and 6, 6, 0.9, 0.5, 5 µl/ml for B. subtilis. Time-kill kinetics evaluation showed that the adducts possess bacteriostatic action. Further it was evaluated for high-throughput in vitro assays to determine the compatibility of the adducts for drug delivery. The haemolytic and thrombolytic activity was analysed against normal mouse erythrocytes. The haemolytic activity showed prominent results, and thereby projecting this acrylonitrile adducts as potent antimicrobial and haemolytic agent.

Biocompatible Aza-BODIPY-Biotin Conjugates for Photodynamic Therapy of Cancer.

With an objective to develop efficient photosensitizers to cancerous tissues, we synthesized two novel biocompatible sensitizers based on aza-BODIPYs incorporated with heavy atoms and biotin moieties. The bioconjugates DPR2a and DPR2b exhibited a favorable absorption range (600-750 nm) with excellent triplet-state quantum yields (up to 79%) and singlet oxygen generation yields (up to 75%). In vitro photobiological investigations employing MDA-MB-231 breast cancer cell lines exhibited rapid cellular uptake, negligible dark toxicity, and high photocytotoxicity. The mechanism of cell death of these systems was predominantly due to the mitochondrial damage, leading to apoptosis mediated via the generation of singlet oxygen-triggered reactive oxygen species. The in vivo studies with the representative conjugate DPR2a employing female NOD/SCID mice models showed inhibition in tumor growth and significantly decreased tumor volume post photodynamic therapy (PDT) treatment. Our results validate that both DPR2a and DPR2b with iodine incorporation exhibit favorable and superior photophysical and photobiological aspects and demonstrate thereby their potential applications in imaging and PDT of cancer.

A Versatile Pd-Catalyzed Alkyne Annulation Process for Benzo[a]carbazoles and their Anticancer Analogues.

A Pd-catalyzed, simple, and divergent approach for the direct synthesis of benzo[a]carbazoles from internal alkynes and N-tosyl-iodoindoles has been demonstrated. This methodology highlights the influences of reaction media and temperature for the synthesis of either N-protected or N-deprotected benzo[a]carbazoles. This cascade strategy provides a series of electronically different benzo[a]carbazoles with good yields. The synthesized benzo[a]carbazoles were evaluated for in vitro anticancer activity against human lung cancer A549 cells and human breast cancer MDA-MB-231 cells. Notably, two of the representative analogues displayed potent anticancer activity against both cancer cell lines.

Evaluation of water quality index and geochemical characteristics of surfacewater from Tawang India.

In this study,the water samples were collected from 31 sites of Tawang, Arunachal Pradesh, India (North-Eastern Himalaya), during the winter season to check the suitability of water for drinking and irrigation purposes.The study scientifically demonstrates the estimation of Water quality index (WQI) andhydrogeochemical characteristics of surface water samples by utilizing multivariate statistical methods. The main water quality parameters considered for this study were TDS, conductivity, salinity, pH, hardness, cations and anions. WQI was calculated in order to find out the deviation in the water quality parameters particularly with respect to BIS permissible limits.The major influencing factors responsible for the variation in these parameters were derived by using Principal component analysis (PCA) and Correlation matrix.To check the suitability of water for drinking purpose, hydrogeochemical facies and rock water interaction was derived by using well established methods such as Piper Plot (determine water type), WQI (Quality monitoring), and saturation index (for mineral dissolution). The results revealed that the silicate weathering was the main ionic source in comparison to carbonate weathering which is due to the higher dissolution capacity of silicate minerals.The results of the scattered plot between (Ca2+ + Mg2+)-(HCO3- + SO42-) versus (Na+ + K+)-Cl- (meq/L) highlighted thation exchange occurs between Mg2+ and Ca2+ofsurface water with Na+ and K+of rock /soil. This means that calcium ion was getting adsorbed, and sodium ion was getting released. The Ca2+-Mg2+-HCO3-, Na+-HCO3-and Na+-Cl- type of surface water suggested permanent and temporary hardness respectively in the studied region. The dominant cations of this study were Na+ and Ca2+ while the dominant anions were HCO3- and SO42-. In order to check the suitability of water sources for irrigation, parameters like, Magnesium hazard (MH), Total hardness (TH), Permeability Index (PI), Kelly Index (KI), Sodium adsorption rate (SAR), Sodium percentage (Na%), and Residual sodium carbonate (RSC) were determined. The results showed that 93% of the samples had PI score < 75, which indicates the suitability of the water for irrigation. Also the WQI calculation showed an average WQI value of 82.49, amongst which 61% samples were in the range of 0-50 being considered as good for drinking, while 39% were catageorised as unsuitable for drinking showing a value of > 50. Hence the above findings reveal that geogenic activities play a major role in influencing the water quality of Tawang region. Hence suitable water treatment technologies or methods might be used to eliminate thenon desirable elements and minerals present in surface water.

Silver-doped active carbon spheres and their application for microbial decontamination of water.

Highly efficient and durable, silver nanoparticles doped Active Carbon Spheres ACS(Ag) were synthesized by carbonization and activation of silver exchanged resins. The silver exchanged resins were prepared by exchanging H+ ions of polystyrene sulphonate resin with Ag+ ions of silver nitrate (AgNO3). The quantity of Ag+ in the spheres was controlled by varying the concentration of AgNO3, from 0.0125 to 0.1 M. With increasing molar concentration of AgNO3, the effective intake of Ag+ by the sphere increases from 1.1 to 8.1 weight percent (wt %). For activation, the spheres were incubated in the CO2 atmosphere for 6 h at fixed soaking temperature i.e. 1123 K. The characterization of synthesized silver doped ACS was performed by using different sophisticated instrumental techniques. The antimicrobial activity of silver doped ACS was studied against different bacterial strains like, E. coli, B. subtilis and Staphylococcus aureus. The study demonstrated that the zone of inhibition for E. coli was 16.9 ± 0.7 mm while for B. subtilis it was 17.1 ± 0.3 mm at a concentration of 8 mg of synthesized material. In addition, satisfactory results were obtained in shake flask and filtration test experiments also, even at a low concentration of 2 mg, showing growth inhibition of 94% for E. coli and 93% for B. subtilis. When the concentration of silver doped ACS was increased to 8 mg, complete removal of both the bacteria was observed after 24 h (100 % reduction for E. coli and B. subtilis). Furthermore, when silver doped ACS was tested against Staphylococcus aureus according to ASTM:E 2149-01 method, biocidal activity of up to 73% was observed. Therefore, the silver doped ACS can be considered as a potential biocidal material for the studied bacterial strains and hence find suitable application for decontamination of water.

Preparation and chiro-optical characterization of polyaniline doped with (+) or (-)-2-pyrrolidone-5-carboxylic acid (PCA).

Optically active polyaniline (PANI) salts were readily generated in solution via the enantioselective acid doping of neutral emeraldine base (EB) form of PANI with either (+) or (-)-2-pyrrolidone-5-carboxylic acid (PCA) in dimethylsulfoxide (DMSO) and dimethylformamide (DMF) solvents. Strong mirror imaged circular dichroism (CD) spectra were obtained for the deep green polymer solutions obtained with (+) or (-) PCA, suggesting that the acid doping is enantioselective, with one helical screw of the polymer chain being preferentially produced depending on the nature of enantiomer. It was observed that molar concentration of PCA as well as nature of solvent plays a very important role in the generation of optically active PANI. The generated optically active PANI did not show any loss of optical activity up to 200 h.

Iron oxide coated hollow poly(methylmethacrylate) as an efficient adsorption media for removal of arsenic from water.

Adsorption of arsenic onto iron-based adsorption media has been established as a convenient method for the removal of arsenic from contaminated water. The study describes the efficiency of iron oxide coated hollow poly(methyl methacrylate) microspheres (FHM) as an adsorptive media for the removal of arsenic from water. Hollow poly(methyl methacrylate) microspheres (HPMM) were synthesized by solvent evaporation and an electroless plating technique and the surface of the polymer was coated with iron oxide (FeO) particles. Structural characterization was performed using Optical Microscopy (OM), Scanning Electron Microscopy (SEM), Fourier Transform Infrared spectroscopy (FTIR), Energy Dispersive X-ray diffraction (EDAX), and Thermogravimetric Analysis (TGA). A study on the effect of the varying initial concentration of arsenic ions on percentage removal was performed in the laboratory and the adsorption capacity of the adsorbent was measured. Adsorption isotherm studies were carried out to evaluate the adsorption efficiency of FHM in removing arsenic from contaminated water. The Langmuir and Freundlich isotherm models were used to analyze the equilibrium experimental data. The isotherm study revealed that Langmuir adsorption data are well fitted and the maximum adsorption capacity of FHM in removing arsenic is 10.031 mg g-1. This high arsenic uptake capability combined with a low density of FHM makes it a potential material for arsenic removal particularly during the fabrication of lightweight portable water purification devices.

Functionalized carbon nanotubes: synthesis, properties and applications in water purification, drug delivery, and material and biomedical sciences.

Carbon nanotubes (CNTs) are considered as one of the ideal materials due to their high surface area, high aspect ratio, and impressive material properties, such as mechanical strength, and thermal and electrical conductivity, for the manufacture of next generation composite materials. In spite of the mentioned attractive features, they tend to agglomerate due to their inherent chemical structure which limits their application. Surface modification is required to overcome the agglomeration and increase their dispersability leading to enhanced interactions of the functionalized CNTs with matrix materials/polymer matrices. Recent developments concerning reliable methods for the functionalization of carbon nanotubes offer an additional thrust towards extending their application areas. By chemical functionalization, organic functional groups are generated/attached to the surfaces as well as the tip of CNTs which opens up the possibilities for tailoring the properties of nanotubes and extending their application areas. Different research efforts have been devoted towards both covalent and non-covalent functionalization for different applications. Functionalized CNTs have been used successfully for the development of high quality nanocomposites, finding wide application as chemical and biological sensors, in optoelectronics and catalysis. Non covalently functionalized carbon nanotubes have been used as a substrate for the immobilization of a large variety of biomolecules to impart specific recognition properties for the development of miniaturized biosensors as well as designing of novel bioactive nanomaterials. Functionalized CNTs have also been demonstrated as one of the promising nanomaterials for the decontamination of water due to their high adsorption capacity and specificity for various contaminants. Specifically modified CNTs have been utilized for bone tissue engineering and as a novel and versatile drug delivery vehicle. This review article discusses in short the synthesis, properties and applications of CNTs. This includes the need for functionalization of CNTs, methods and types of functionalization, and properties of functionalized CNTs and their applications especially with respect to material and biomedical sciences, water purification, and drug delivery systems.

Smart pH-Responsive Polyaniline-Coated Hollow Polymethylmethacrylate Microspheres: A Potential pH Neutralizer for Water Purification Systems.

Smart materials with potential pH controllability are gaining widespread concern due to their versatile applicability in water purification systems. A study presented here demonstrates a successful synthesis of smart pH-responsive polyaniline (PANI)-coated hollow polymethylmethacrylate microspheres (PHPMs) using a combination of solvent evaporation and in situ coating techniques. The material was characterized by using conventional techniques. Images recorded by an optical microscope displayed clear evidence in support of the coating, which was further supported by the SEM images. Surface roughness due to the coating was distinct in the SEM images. The PANI coating has enabled the microsphere to effectively neutralize the pH of water in water purification systems, which is very important in tackling the excessive acidic or basic problem of water resources. This study introduces a simple, facile, and cost-effective synthetic route to develop polyaniline-coated hollow polymethylmethacrylate microspheres with high performance as a pH-responsive material for water purification. The low density of the material and relatively large surface area compared to conventionally used chemicals further enhance the application prospect of the material.